Synthesis and Application of Chiral Spiro[chroman-4,1'-indane] Bidentate Ligand Iridium Complexes

Abstract

The present invention relates to the synthesis and application of a chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex. The synthesis method uses ( R / S )-2-oxospiro[chroman-4,1'-dihydroindene]-7'-ol as the starting material, and the corresponding chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand can be conveniently synthesized through trifluoromethanesulfonic acid esterification, palladium-catalyzed coupling and silane reduction. This ligand can be complexed with an iridium metal precursor to obtain a catalyst; the obtained chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium catalyst can be applied to the asymmetric catalytic hydrogenation reaction of β,β-disubstituted acrylate compounds (or β,β-disubstituted acrylic acid and a base) to efficiently and highly selectively obtain chiral carboxylic acids. The catalyst dosage can be reduced to 0.02 mol%, and a yield of 99% and an ee of 97% can be achieved. This is the best result of asymmetric catalytic hydrogenation that can be obtained for this type of compound so far. This catalyst and the hydrogenation method have important application value and potential in the asymmetric synthesis of chiral drugs, natural products and flavors and fragrances.

Description

Technical Field

[0001] The present invention relates to the synthesis and application of a novel chiral spiro[chroman-4,1'-indan] bidentate ligand iridium complex. This chiral spiro[chroman-4,1'-indan] bidentate ligand iridium complex can be used as a chiral catalyst in asymmetric catalytic reactions and has high application value in the field of asymmetric catalysis, belonging to the field of asymmetric catalysis. Background Art

[0002] Currently in industrial production, there is a high demand for β-chiral propionic acid compounds. The most efficient method for preparing such compounds is the asymmetric catalytic hydrogenation of β,β-disubstituted acrylate compounds. For this reaction, there are currently only three catalytic systems: bisphosphine ligand ruthenium complex (Ohta, T.; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R. J. Org. Chem. 1987, 52 , 3174–3176.), bisphosphine ligand rhodium complex (Yan, Q.; Kong, D.; Zhao, W.; Zi, G.; Hou, G. J. Org. Chem. 2016, 81 , 2070–2077.), and phosphite rhodium complex (Li, Y.; Dong, K.; Wang, Z.; Ding, K. Angew. Chem. Int. Ed. 2013, 52 , 6748–6752.). The current dosage of these three catalysts is very high (0.2–1 mol%), which cannot meet the requirements of actual production. To solve this problem, a new class of chiral spiro[chroman-4,1'-indan] bidentate ligand iridium complexes needs to be designed and synthesized.

[0003] Chinese Patent CN 109970697 B discloses a synthesis method of a chiral spiro[chroman-4,1'-indan] molecule, which is of great significance for studying and discovering the practical uses and application values of chiral spiro[chroman-4,1'-indan] molecules. This new ligand and catalyst are simple to synthesize, have stable properties, a wide range of substrate applications, and high enantioselectivity. Based on the synthesis of chiral spiro[chroman-4,1'-indan] bidentate ligand iridium complexes, for β,β-disubstituted acrylate compounds, a turnover number greater than 5000, a yield of 99%, and an enantioselectivity of 97% can be achieved, which has extremely high research and application value. Summary of the Invention

[0004] The present invention aims to provide the synthesis and application of a chiral spiro[chroman-4,1'-dihydroindene] bidentate iridium complex. This chiral spiro[chroman-4,1'-dihydroindene] bidentate iridium complex can be used as a catalyst in the asymmetric catalytic hydrogenation of β,β-disubstituted acrylates (or β,β-disubstituted acrylic acid and a base), resulting in chiral carboxylic acids with high efficiency and selectivity. The catalyst dosage can be reduced to 0.02 mol%, achieving a 99% yield and 97% ee, representing the best asymmetric catalytic hydrogenation results achieved to date. This chiral spiro[chroman-4,1'-dihydroindene] bidentate iridium complex catalyst and hydrogenation method have significant application value and potential in the asymmetric synthesis of chiral pharmaceuticals, natural products, and flavors and fragrances.

[0005] The chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex provided by the present invention has the following general formula (I):

[0006]

[0007] In the general formula (I):

[0008] R 1 is an aryl group, R 2 Halogen atoms, carboxyl groups, BF4 - PF6 - 、[Rh(cod)2]SbF6 - 、OTf - .

[0009] The above term alkyl is preferably methyl, ethyl, propyl, butyl, etc.;

[0010] The aryl group is preferably a phenyl group which may be substituted or unsubstituted by an alkyl group or an alkoxy group. The alkyl group is as defined above, and the alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like.

[0011] The bidentate ligand iridium complex is recorded as (±) chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex, (-) chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex, and (+) chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex.

[0012] The method for synthesizing the chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex provided by the present invention comprises the steps of:

[0013]

[0014] The specific steps are:

[0015] Step 1: Starting material ( R / S)-7′-hydroxy-2′,3′-dihydrospiro[chroman-4,1′-indene]-2-one( R / S )-1 is reacted with a triflate reagent in an organic solvent at a temperature range of 0-60 °C under the promotion of a base to obtain ( R / S )-7'-trifluoromethylsulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one ( R / S )-2.

[0016] The organic solvent is one or more of dichloromethane, toluene, tetrahydrofuran, and methanol; the base is triethylamine, diisopropylethylamine, potassium carbonate, cesium carbonate, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, and dimethylaminopyridine; and the triflate reagent is trifluoromethanesulfonic anhydride and N-phenylbis(trifluoromethanesulfonyl)imide.

[0017] Step 2: ( R / S )-7'-trifluoromethylsulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one ( R / S )-2 undergoes a coupling reaction with diarylphosphine oxide in the presence of an organic solvent, a base, and a temperature range of 0-160 °C under the catalysis of a phosphine ligand and palladium acetate, and is subsequently reduced under the conditions of silane and a base to obtain the target ligand ( R / S )-7'-diarylphosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one ( R / S )-II.

[0018] The aryl group in the diarylphosphine oxide is a phenyl group substituted or unsubstituted by an alkyl group or an alkoxy group; the alkyl group is methyl, ethyl, propyl, butyl, or an aryl-substituted methyl group; the alkoxy group is methoxy, ethoxy, propoxy, or butoxy. The organic solvent is one or more of dichloromethane, toluene, tetrahydrofuran, and methanol; the base is triethylamine, diisopropylethylamine, potassium carbonate, cesium carbonate, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, or dimethylaminopyridine; the phosphine ligand is a common bisphosphine ligand such as 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, and 1,1'-binaphthyl-2,2'-bisdiphenylphosphine; and the silane is diphenylsilane or trichlorosilane.

[0019] Step 3: Ligand ( R / S )-7'-diarylphosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one ( R / S )-II reacts with an iridium metal precursor in an organic solvent at a temperature range of 0~60 °C to obtain catalyst (I).

[0020] The organic solvent is one or more of dichloromethane, toluene, tetrahydrofuran, and methanol, and the iridium metal precursor is [Ir(cod)Cl]2 (cod = cyclooctadiene), [Ir(cod)2]BF4, [Ir(cod)2]PF6, [Ir(cod)2]SbF6, [Ir(cod)2]OTf).

[0021] The present invention provides the use of the aforementioned chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex (I) as a catalyst and the ligand of formula (II) in asymmetric catalytic reactions. The asymmetric reactions include hydrogenation reaction, hydroformylation reaction, hydrosilylation reaction, hydroboration reaction, hydroxyhydrogenation reaction, hydroamination reaction, hydrocyanation reaction, isomerization formylation reaction, hydroaminomethylation reaction, transfer hydrogenation reaction, allylation reaction, olefin metathesis reaction, ring isomerization reaction, Diels-Alder reaction, asymmetric coupling reaction, Aldol reaction, Michael addition reaction, asymmetric epoxidation reaction, kinetic resolution, and [m+n] cyclization reaction.

[0022] According to the aforementioned use, the catalyst has high activity and enantioselectivity for the hydrogenation of β,β–disubstituted acrylic acid and β,β–disubstituted acrylate compounds in an organic solvent, and an optically active chiral carboxylate is obtained. The catalytic hydrogenation reaction process is as follows:

[0023]

[0024] Under the protection of argon or nitrogen, in an organic solvent, and stirred at 0~100 °C for 3~200 hours to obtain an optically active chiral carboxylic acid.

[0025] The specific steps are: under the protection of argon or nitrogen, add carboxylate (or carboxylic acid and base), catalyst (I) (or ligand II and metal precursor) to a hydrogenation autoclave, then add an organic solvent and stir to dissolve, charge hydrogen and react within the temperature range of 0~100 °C and stir at a hydrogen pressure of 2~100 atm for 3~200 hours to obtain an optically active chiral carboxylate; wherein the iridium metal precursor is [Ir(cod)Cl]2 (cod = cyclooctadiene), [Ir(cod)2]BF4, [Ir(cod)2]PF6, [Ir(cod)2]SbF6, [Ir(cod)2]Otf.

[0026] The organic solvent is one or more of dichloromethane, toluene, tetrahydrofuran, methanol, ethanol, isopropanol, and tert-butanol. In the general formula (III): R 3 、R 4 、R 5is a hydrogen atom, a halogen atom, a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C2-C8 alkenyl group, a C5-C 14 arylalkyl group, a C6-C 12 arylalkenyl group, a -C1-C8 alkoxy group, an aryloxy group; R 6 is a hydrogen atom, a sodium atom, a potassium atom, a lithium atom, a calcium atom; when R 6 is a hydrogen atom, a base such as triethylamine, diisopropylethylamine, sodium carbonate, cesium carbonate, potassium carbonate needs to be added; the configuration of the obtained chiral carboxylic acid can be either the ( R )-configuration or the ( S )-configuration; when the catalyst dosage is low (substrate / catalyst > 500), 1-5% mol% of an acid such as acetic acid, formic acid, hydrochloric acid, sulfuric acid or the conjugate acid corresponding to the substrate needs to be added to the reaction system.

[0027] The present invention provides the synthesis and application of a chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex. Its characteristics are: 1) The chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex has central chirality, so there are left-handed chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complexes and right-handed chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complexes. The racemic spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex can be synthesized from the racemic spiro[chroman-4,1'-dihydroindene] monophenol as a raw material. 2) The present invention can be used as a chiral catalyst in asymmetric hydrogenation. This compound has high activity and enantioselectivity in the asymmetric catalytic hydrogenation of β,β–disubstituted acrylate compounds in organic solvents, achieving the highest catalyst efficiency and turnover number reported in the current literature.

[0028] The chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex can be used as a catalyst in the asymmetric catalytic hydrogenation reaction of β,β–disubstituted acrylate compounds (or β,β–disubstituted acrylic acid and a base), so as to efficiently and highly selectively obtain chiral carboxylic acids. The catalyst dosage can be reduced to 0.02 mol%, and a yield of 99% and an ee of 97% can be achieved, which is the best result of asymmetric catalytic hydrogenation obtained so far. And the chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex catalyst and the hydrogenation method have important application values and potentials in the asymmetric synthesis of chiral drugs, natural products and fragrances. Detailed implementation mode

[0029] The present invention is further illustrated by the following examples. However, the following examples only help to further understand the present invention and cannot limit the content of the present invention. For the experimental methods without specific conditions noted in the examples, they are usually carried out according to the conventional conditions and the conditions described in the manuals, or according to the conditions recommended by the manufacturers; for the general equipment, materials, reagents, etc., without special instructions, they can be obtained from commercial channels.

[0030] Example 1: R )-7'-Trifluoromethylsulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0031]

[0032] Take R )-Spiro[chroman-4,1'-dihydroindene] monophenol a (1.28 g, 4.8 mmol) in a 100 ml dry Schlenck flask, replace the atmosphere in the flask with argon, then add dichloromethane (20 mL) and pyridine (0.69 mL, 8.5 mmol), stir to dissolve and cool to 0 °C in an ice bath. Then add trifluoromethanesulfonic anhydride (0.97 mL, 5.8 mmol). Stir the reaction at room temperature naturally, monitor the reaction by TLC (PE / EA = 10:1), after the raw materials disappear, add saturated copper sulfate solution (5 mL) to quench the reaction, extract the aqueous phase with dichloromethane (20 mL×2), wash the organic phase with saturated brine, then dry with anhydrous sodium sulfate, remove the solvent under vacuum, and separate and purify by column chromatography (PE / EA = 10:1 to 5:1) to obtain the target product R )-7'-Trifluoromethylsulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one, 1.89 g, yield 99%, white solid, melting point: 81–82 °C, optical rotation: [a]26D = –130 ( c 0.1, CHCl3), 1 1H NMR (400 MHz, CDCl3) δ7.46 (t, J J = 7.8 Hz, 1H), 7.40 (d, J J = 7.5 Hz, 1H), 7.36–7.22 (m, 2H), 7.15(d, J J = 8.1 Hz, 1H), 7.06 (t, J J = 7.5 Hz, 1H), 6.68 (dd, J J = 7.7, 1.6 Hz,1H), 3.43 (d, J= 15.5 Hz, 1H), 3.09 (td, J = 7.3, 3.8 Hz, 2H), 2.94 (d, J =15.5 Hz, 1H), 2.48–2.36 (m, 1H), 2.32–2.20 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ166.8, 150.3, 148.8, 146.1, 134.9, 130.8, 129.0, 127.8, 125.6, 125.0, 124.8,119.5, 118.0 (q, J = 319.9 Hz), 117.33, 50.24, 40.69, 39.27, 30.44. HRMS(ESI) Calcd for C 18 H 13 F3NaO5S + ([M+Na] + ): 421.0333; Found: 421.0331.

[0033] Among them, ( R )-spiro[chroman-4,1'-indan] monophenol a was prepared according to Chinese Patent CN 109970697 B (also refer to the application filed on the same day by the applicant, with the invention title: Synthesis and Application of Chiral Spiro[chroman-4,1'-indan] Phosphite Monophosphorus Ligand). The specific synthesis route is as follows:

[0034]

[0035] Step 1: Weigh 3-(3-hydroxyphenyl)propionic acid (37.3 g, 224 mmol) into a dry 2000 mL reaction flask, add dichloromethane (300 mL) and acetonitrile (150 mL), and stir to dissolve at room temperature. Use an ice-water bath to cool the system to below 5 °C, and then use a constant-pressure dropping funnel to dropwise add a dichloromethane solution of bromine (11.5 mL Br2 plus 150 mL dichloromethane), and finish dropping in 1 hour. Then continue to stir and react for 1.5 hours under the condition of an ice-water bath. After monitoring the reaction by 1H NMR and the reaction is completed, quench the system with saturated sodium thiosulfate solution, remove the solvent under reduced pressure, dissolve and dilute with ethyl acetate (500 mL), separate the layers, extract the aqueous phase with ethyl acetate (150 mL × 2), combine the organic phases, dry with anhydrous magnesium sulfate, filter by suction, and remove the solvent to obtain 3-(2-bromo-5-hydroxyphenyl)-propionic acid: light yellow solid, 54.3 g, yield 99%, melting point: 152 - 155 °C (can be directly used for the next step without purification).1 1H NMR (400 MHz, CD3OD) δ: 7.30 (d, J J = 8.6 Hz, 1H), 6.77 (s,1H), 6.57 (d, J J = 8.7 Hz, 1H), 5.02 (brs, 2H), 2.94 (t, J J = 7.8 Hz, 2H), 2.59(t, J J = 7.8 Hz, 2H). 13 13C NMR (101 MHz, CD3OD) δ 175.0, 156.8, 140.6, 133.0,116.9, 115.0, 112.5, 33.5, 31.1.

[0036] Step 2: Add 3-(2-bromo-5-hydroxyphenyl)-propionic acid (40 g, 163 mmol) and carbonyldiimidazole CDI (28.6 g, 176 mmol) into a 3000 mL dry reaction flask, and dissolve them with tetrahydrofuran (700 mL). Replace the atmosphere with argon, and stir the reaction at room temperature for 8 hours. Add a solution of magnesium monoethyl malonate (39 g, 253 mmol) in tetrahydrofuran (300 mL) to the reaction system, and continue to stir the reaction at room temperature for 12 hours. Monitor the reaction completion by TLC. Acidify the system with 1N HCl, extract with diethyl ether (2 × 150 mL), combine the organic phases, then wash with saturated sodium chloride aqueous solution and dry with anhydrous sodium sulfate. Filter by adding diatomaceous earth, remove the solvent under reduced pressure, and perform column chromatography (petroleum ether / ethyl acetate = 5:1) to obtain ethyl 5-(2-bromo-5-hydroxyphenyl)-3-oxopentanoate b: a light yellow foamy solid, 39 g, with a yield of 76%. 1 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J J = 8.7 Hz, 1H), 6.66 (d, J J = 3.0 Hz, 1H), 6.50 (dd, J J = 8.7, 3.1Hz, 1H), 4.04 (q, J J = 7.2 Hz, 2H), 3.63 (s, 3H), 3.31 (s, 2H), 2.84 (ddd, J J =9.3, 7.4, 2.1 Hz, 2H), 2.78–2.72 (m, 2H), 1.13 (t, J J = 7.1 Hz, 3H).13 C NMR (101 MHz, CDCl3) δ 202.4, 167.5, 155.5, 140.7, 133.6, 117.6, 115.5, 114.2, 61.7, 49.3, 42.7, 30.0, 14.1.

[0037] Step 3: Add ethyl 5-(2-bromo-5-hydroxyphenyl)-3-oxopentanoate b (17.8 g, 56.5 mmol) to a 1000 mL dry reaction flask, and dissolve it with dichloromethane (300 mL). Replace the atmosphere in the system with argon, and use an ice-water bath to control the temperature in the system below 5 °C. Then slowly add dropwise trifluoromethanesulfonic acid (15.0 mL, 169 mmol). After the addition is complete, remove the ice bath, and stir the system at room temperature for 0.5 h. Monitor by TLC until all the raw materials are completely converted, and a large amount of yellow solid precipitates in the system. Add resorcinol (6.2 g, 56.5 mmol) to the reaction system, and continue to stir the reaction at room temperature for 1 h. Monitor by TLC until all the intermediates are completely converted. Quench the reaction with ice water, extract with ethyl acetate (2 × 150 mL), combine the organic phases, wash with saturated sodium chloride aqueous solution, dry the organic phase with anhydrous magnesium sulfate, filter with diatomaceous earth, remove the solvent under reduced pressure, and perform column chromatography (petroleum ether / ethyl acetate = 5:1). Obtain 4'-bromo-5-hydroxy-7'-hydroxy-spiro[chroman-4,1'-dihydroindene]-2-one c: yellow foamy solid, 16.9 g, with a yield of 83%. 1 H NMR (400 MHz, CDCl3) δ 7.38 (d, J J = 8.9 Hz, 1H), 6.79 (d, J J = 9.0 Hz, 1H), 6.65 (d, J J = 8.5 Hz, 1H), 6.55 (d, J J = 2.3 Hz, 1H), 6.39–6.33 (dd, 1H), 3.42 (d, J J = 15.8 Hz, 1H), 3.30–3.13 (m, 1H), 2.94–2.83 (m, 2H), 2.78 (d, J J = 15.9 Hz, 1H), 2.56–2.49 (m, 1H), 2.28 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ170.5, 158.8, 155.2, 152.4, 146.9, 133.3, 132.8, 127.5, 121.5, 117.1, 112.7, 108.8, 104.7, 54.8, 51.4, 40.9, 40.8, 33.1.

[0038] Step 4: Add 4'-bromo-5-hydroxy-7'-hydroxy-spiro[chroman-4,1'-dihydroindene]-2-one c (6.8 g, 18.8 mmol) to a 250 mL dry reaction flask, dissolve it in dichloromethane (120 mL), and then add pyridine (3.0 mL, 37.6 mmol). Place the system in an ice-water bath to cool the temperature of the system below 5 °C, and then slowly add trifluoromethanesulfonic anhydride (3.2 mL, 18.8 mmol) dropwise. After the dropwise addition, remove the ice bath and stir the reaction at room temperature for 12 hours. Monitor the reaction by TLC until all the raw materials are completely converted. Quench the reaction with ice water, extract with ethyl acetate (2 × 50 mL), combine the organic phases, wash with saturated sodium chloride aqueous solution, dry the organic phase with anhydrous magnesium sulfate, filter through diatomaceous earth, remove the solvent under reduced pressure, and perform column chromatography (petroleum ether / ethyl acetate = 10:1). Obtain 4'-bromo-5-trifluoromethanesulfonyloxy-7'-hydroxy-spiro[chroman-4,1'-dihydroindene]-2-one d: yellow foamy solid, 7.0 g, yield 76%. 1 H NMR (400 MHz, CDCl3) δ 7.35 (d, J J = 8.4 Hz, 1H), 7.06 (d, J J = 2.4 Hz, 1H), 6.95 (dd, J J = 8.6, 2.5 Hz, 1H), 6.87 (d, J J = 8.6 Hz, 1H), 6.58 (dd, J J = 8.5, 0.8 Hz, 1H), 5.55 (s, 1H), 3.58 (d, J J = 16.0 Hz, 1H), 3.11–2.96 (m, 2H), 2.87 (d, J J = 16.0 Hz, 1H), 2.36 (m, J J = 13.3, 8.6, 6.9 Hz, 1H), 2.25–2.16 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ167.3, 151.9, 150.9, 148.6, 146.2, 133.0, 130.2, 129.6, 127.3, 120.2, 117.4, 116.4, 110.8, 110.7, 50.4, 39.3, 39.0, 32.3.

[0039] Step 5: Add 4'-bromo-5-trifluoromethanesulfonyloxy-7'-hydroxy-spiro[chroman-4, 1'-dihydroindene]-2-one d (19.6 g, 39.7 mmol) to a 500 mL dry reaction flask, dissolve it in anhydrous ethanol (230 mL), then add triethylamine (14 mL, 100 mmol) and 10% Pd / C (2.0 g, 1.9 mmol), and displace the H2 atmosphere. Under the condition of 1 atm H2, react at room temperature for 48 hours, and monitor the completion of the reaction by 1H NMR. Evaporate the solvent under reduced pressure, dissolve and dilute with ethyl acetate (200 mL), and acidify with 1N HCl until the insoluble matter disappears. Separate the layers, extract the aqueous phase with ethyl acetate (3 × 50 mL), combine the organic phases, wash with saturated sodium chloride aqueous solution, dry the organic phase with anhydrous magnesium sulfate, filter through diatomaceous earth, evaporate the solvent, and wash the solid with ether (3 × 20 mL) to obtain rac )-2-oxospiro[chroman-4, 1'-dihydroindene]-7'-ol rac )-a, 9.6 g, yield 91%. 1 H NMR (400MHz, CDCl3) δ 7.27 (m, 1H), 7.21 (t, J = 7.7 Hz, 1H), 7.12 (dd, J = 8.2, 1.2Hz, 1H), 7.03 (td, J = 7.5, 1.3 Hz, 1H), 6.92 (dd, J = 7.5, 1.0 Hz, 1H), 6.82(dd, J = 7.7, 1.6 Hz, 1H), 6.67–6.62 (m, 1H), 4.90 (s, 1H), 3.54 (d, J = 15.9Hz, 1H), 3.00 (t, J = 7.3 Hz, 2H), 2.84 (d, J = 15.9 Hz, 1H), 2.33 (dt, J =12.8, 7.4 Hz, 1H), 2.24–2.13 (m, 1H).13 13C NMR (101 MHz, CDCl3) δ 168.4, 152.4, 150.7, 146.7, 130.0, 128.7, 125.6, 124.8, 117.7, 117.3, 114.4, 49.3, 40.4, 39.2, 30.6.

[0040] Step 6: Weigh ([[]] rac )-2-oxospiro[chroman-4,1'-dihydroindene]-7'-ol ([[]] rac )-a (7.0 g, 26.3 mmol) and N -benzylchlorocinchonidine e (3.2 g, 7.5 mmol) into a 250 mL dry reaction flask in sequence, place a magnetic stir bar, and add dry tert-butyl methyl ether (130 mL). Place the reaction system into an oil bath preheated to 60 °C for reflux, set the magnetic stirring speed of the stirrer to 1000 r / min, and stir continuously for 24 hours. A large amount of white insoluble matter forms in the system. After the system cools to room temperature, filter by suction to separate the filtrate and the insoluble matter. Mother liquor recovery: Wash the insoluble matter with ethyl acetate (3 × 20 mL), combine the filtrate and the washing liquid, and evaporate under reduced pressure to obtain the ([[]] S )-a that has not formed an inclusion complex with the resolving agent. Yield: 62%, 62% ee R Dissociation of the inclusion complex: Place the insoluble matter in a 250 mL beaker, dilute it with ethyl acetate (80 mL), and continuously add 1N HCl until no insoluble matter remains. Separate the layers using a separatory funnel, extract the aqueous phase with ethyl acetate (2 × 50 mL), combine the organic phases, dry over anhydrous magnesium sulfate, filter by suction with diatomaceous earth, and evaporate under reduced pressure to obtain the ([[]] R )-a that has formed an inclusion complex with the resolving agent. Yield: 40%, 95% ee R ee ee .

[0041] Recrystallize both using n-hexane-methyl tert-butyl ether as the solvent to obtain ([[]] S )-a with a yield of 36% and an ee value of >99%; ([[]] R )-a with a yield of 34% and >99% ee . HPLC conditions: Chiralcel IC-3 column (25 cm × ø0.46 cm); n- hexane / 2-propanol = 85:15; temp, rt; flow rate = 1.0 mL / min; 88 bars; 220 nm UV detector.

[0042] ​​Example 2: R )-7'-Diphenylphosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0043]

[0044] Take R )-7'-Trifluoromethanesulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one (80 mg, 0.2 mmol), 1,3-bis(diphenylphosphino)propane (4.2 mg, 0.01 mmol), palladium acetate (1.7 mg, 0.01 mmol) into a 50 ml dry Schlenk flask, displace the atmosphere in the flask with argon, then add dimethyl sulfoxide (10 mL) and diisopropylethylamine (155 mg, 1.2 mmol), stir to dissolve and degas. Then heat the reaction at 95 °C. Monitor the reaction by TLC (PE / EA = 10:1). After the raw materials disappear, cool to room temperature, add saturated ammonium chloride (2 mL) to quench the reaction, wash the organic phase with 1N HCl (10 mL), extract the aqueous phase with ethyl acetate (20 mL×2), wash the organic phase with saturated NaHCO3 and saturated brine, then dry with anhydrous sodium sulfate, remove the solvent under vacuum, take the solid into a 100 ml dry sealed tube, displace the atmosphere in the flask with argon, then add toluene (40 mL) and diisopropylethylamine (1.3 g, 10 mmol), cool to 0 °C in an ice bath and then dropwise add trichlorosilane (271 mg, 2 mmol). After refluxing for 3 days, cool to 0 °C, add saturated sodium bicarbonate solution (2 mL) to quench the reaction, add diatomaceous earth and ethyl acetate (20 mL), stir, after no bubbles are generated in the system, filter off the solid, and wash the solid with ethyl acetate (10 mL×2), remove the solvent under vacuum, and separate and purify by column chromatography (PE / EA = 50:1–20:1) to obtain the target ligand. White solid, 81 mg, yield 93%, 1 1H NMR (400 MHz, CDCl3) δ 7.34 (d, J J = 7.4 Hz, 1H), 7.30–7.19 (m, 7H), 7.17–7.02 (m, 7H), 6.57 (td, J J = 7.3, 1.7Hz, 1H), 6.48 (dd, J J = 7.6, 1.7 Hz, 1H), 4.28–4.15 (m, 1H), 3.10–2.91 (m,2H), 2.86 (d, J= 15.4 Hz, 1H), 2.43–2.30 (m, 1H), 2.23–2.11 (m, 1H). 13 C NMR(101 MHz, CDCl3) δ 167.7, 150.2, 149.4, 149.2, 145.2, 145.1, 137.5, 137.4,136.0, 135.9, 135.7, 135.7, 133.7, 133.6, 133.5, 133.4, 133.0, 132.9, 130.7,128.7, 128.6, 128.5, 128.4, 128.3, 128.3, 128.1, 127.1, 127.1, 126.1, 124.1,116.9, 51.6, 41.8, 41.6, 40.8, 30.0. 31 P NMR (162 MHz, CDCl3) δ -22.29. Optical rotation: [a]27D = –128 ( c 0.1, CHCl3), melting point: 205–206 °C, HRMS (ESI) Calcd for C 29 H 24 O2P + ([M+H] + ): 435.1508; Found: 435.1512.

[0045] Example 3: ( R )-7'-Bis(3,5-dimethylphenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0046] The operation was the same as in Example 2, white solid, 87 mg, yield 88%. 1 H NMR (400 MHz, CDCl3) δ: 1 H NMR (400 MHz, CDCl3) δ 7.36–7.23 (m, 2H), 7.20–7.03 (m, 3H), 6.90 (d, J =6.6 Hz, 2H), 6.68 (t, J = 8.2 Hz, 4H), 6.58 (td, J = 7.4, 1.5 Hz, 1H), 6.42(dd, J = 7.7, 1.5 Hz, 1H), 4.33 (dd, J= 15.5, 10.7 Hz, 1H), 3.09–2.91 (m, 3H), 2.85 (d, J = 15.4 Hz, 1H), 2.42–2.31 (m, 1H), 2.20 (s, 12H). 13 C NMR (101 MHz, CDCl3) δ 167.9, 150.2, 149.1, 148.8, 145.0, 145.0, 137.8, 137.7, 137.5, 137.4, 137.1, 137.1, 135.6, 135.5, 131.7, 131.5, 130.7, 130.7, 130.5, 130.4, 130.1, 128.5, 127.9, 127.2, 127.2, 125.8, 123.9, 116.8, 51.6, 51.6, 41.9, 41.7, 40.9, 30.0, 26.9, 21.3, 21.3. 31 P NMR (162 MHz, CDCl3) δ -22.38. Optical rotation: [a]27D = –129 ( c 0.25, CHCl3), melting point: 84–85 °C HRMS (ESI) Calcd for C 33 H 32 O2P + ([M+H] + ): 491.2134; Found: 491.2133.

[0047] Example 4: ( R )-7'-Bis(3,5-di-tert-butylphenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0048] The operation is the same as in Example 2, white solid, 111 mg, yield 84%. 1 H NMR (400 MHz, CDCl3) δ: 1 H NMR (400 MHz, CDCl3) δ 7.36–7.24 (m, 4H), 7.15–7.02 (m, 3H), 7.01–6.84 (m, 4H), 6.55–6.46 (m, 1H), 6.46–6.37 (m, 1H), 4.42 (dd, J = 15.5, 10.8 Hz, 1H), 3.16–2.93 (m, 2H), 2.87 (d,J = 15.5 Hz, 1H), 2.49–2.30 (m, 1H), 2.24–2.10(m, 1H), 1.19 (d, J = 8.5 Hz, 36H). 13 C NMR (101 MHz, CDCl3) δ 168.0, 150.4,150.3, 150.3, 150.2, 149.0, 148.7, 144.9, 144.8, 136.3, 136.2, 135.5, 135.5,135.1, 135.0, 134.9, 134.7, 130.6, 128.2, 128.0, 127.8, 127.6, 127.4, 127.3,127.2, 125.7, 123.8, 122.2, 122.0, 116.8, 51.6, 51.5, 41.8, 41.6, 40.9, 34.8,34.8, 31.4, 31.3, 30.0. 31 P NMR (162 MHz, CDCl3) δ -20.13. Optical rotation: [a]27D =–96 ( c 0.25, CHCl3), melting point: 85–87 ℃ HRMS (ESI) Calcd for C 45 H 56 O2P + ([M+H] + ): 659.4012; Found: 659.4007.

[0049] Example 5: Synthesis of ( R )-7'-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chroman-[-4,1'-indene]-2-one:

[0050] The operation was the same as in Example 2, white solid, 114 mg, yield 79%. 1 H NMR (400 MHz, CDCl3) δ: 1 H NMR (400 MHz, CDCl3) δ 7.38–7.24 (m, 2H), 7.13–6.99 (m, 3H), 6.86 (d, J =8.2 Hz, 4H), 6.60–6.47 (m, 1H), 6.40 (d, J = 6.8 Hz, 1H), 4.43 (dd, J= 15.6, 10.9 Hz, 1H), 3.65 (d, J = 2.4 Hz, 6H), 3.12–2.93 (m, 2H), 2.87 (d, J = 15.5 Hz, 1H), 2.47–2.30 (m, 1H), 2.26–2.10 (m, 1H), 1.28 (d, J = 7.9 Hz, 36H). 13 C NMR (101 MHz, CDCl3) δ 168.0, 160.0, 159.7, 150.2, 148.8, 148.6, 144.9, 144.8, 143.4, 143.3, 143.2, 143.1, 135.2, 135.2, 135.0, 134.8, 132.0, 131.8, 131.6, 131.4, 130.5, 130.5, 130.4, 129.5, 129.4, 128.1, 127.9, 127.3, 127.3, 125.7, 123.6, 116.7, 64.2, 64.2, 51.5, 51.5, 41.6, 41.4, 40.9, 35.7, 35.7, 31.9, 31.9, 30.0. 31 P NMR (162 MHz, CDCl3) δ -22.50. Optical rotation: [a]27D = –64 ( c 0.1, CHCl3), melting point: 168–169 °C HRMS (ESI) Calcd for C 47 H 60 O4P + ([M+H] + ): 719.4224; Found: 719.4218.

[0051] Example 6: ( R )-7'-bis(3,5-diadamantyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0052] The operation is the same as in Example 2, white solid, 76 mg, yield 37%. 1 H NMR (400 MHz, CDCl3) δ: 11H NMR (400 MHz, CDCl3) δ 7.38–7.27 (m, 2H), 7.12–6.97 (m, 3H), 6.83 (dd, J J =8.0, 2.8 Hz, 4H), 6.47 (ddd, J J = 8.2, 6.0, 2.6 Hz, 1H), 6.37 (d, J J = 7.6 Hz,1H), 4.50 (dd, J J = 15.6, 11.1 Hz, 1H), 3.63 (d, J J = 1.6 Hz, 6H), 3.03 (h, J J =8.8 Hz, 2H), 2.89 (d, J J = 15.6 Hz, 1H), 2.39 (ddd, J J = 12.9, 8.2, 6.3 Hz,1H), 2.17 (ddd, J J = 12.9, 8.3, 6.4 Hz, 1H), 2.09–1.85 (m, 36H), 1.70 (dd, J J =11.8, 3.1 Hz, 24H). 13 13C NMR (101 MHz, CDCl3) δ 168.2, 160.9, 160.6, 150.1,148.8, 148.5, 144.9, 144.8, 143.4, 143.3, 143.2, 143.1, 135.3, 135.2, 135.0,131.7, 131.5, 131.4, 131.2, 130.4, 130.3, 129.4, 129.4, 128.0, 127.9, 127.4,127.4, 125.6, 123.7, 116.7, 65.8, 65.7, 51.5, 51.5, 42.7, 42.6, 41.5, 41.3,40.9, 38.5, 36.9, 36.8, 30.1, 29.2, 29.2. 31 31P NMR (162 MHz, CDCl3) δ -22.38, Optical rotation: [α]27D =–52 ( c c = 0.1, CHCl3), Melting point: 225–226 °C HRMS (ESI) Calcd for C 71 H 84 O4P+ ([M+H] + ): 1031.6102; Found: 1031.6097

[0053] Example 7: ( R Synthesis of 7'-bis(3,5-ditrimethylsilylphenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one:

[0054] The operation was the same as in Example 2, white solid, 89 mg, yield 55% 1 H NMR (400 MHz, CDCl3) δ: 1 HNMR (400 MHz, CDCl3) δ 7.53 (s, 2H), 7.35 (d, J = 7.4 Hz, 1H), 7.28 (t, J =7.7 Hz, 2H), 7.24–7.11 (m, 4H), 7.12–7.04 (m, 2H), 6.56–6.44 (m, 1H), 6.45–6.34 (m, 1H), 4.37 (dd, J = 15.5, 10.6 Hz, 1H), 3.13–2.93 (m, 2H), 2.87 (dd, J = 15.5, 0.9 Hz, 1H), 2.48–2.32 (m, 1H), 2.27–2.12 (m, 1H), 0.15 (d, J =10.4 Hz, 36H). 13 C NMR (101 MHz, CDCl3) δ 167.9, 150.3, 145.1, 139.5, 139.4,139.2, 139.2, 139.1, 138.9, 138.6, 138.4, 138.1, 137.9, 135.7, 135.7, 135.5,135.4, 134.5, 134.4, 134.2, 134.0, 130.7, 128.4, 128.1, 127.3, 127.3, 126.0,123.9, 117.0, 51.7, 41.9, 41.7, 41.0, 30.2, 29.8, –1.0, –1.0. 31 P NMR (162MHz, CDCl3) δ -22.43., Optical rotation: [a]27D = –74 ( c0.1, CHCl3), melting point: 126–127 °C, HRMS(ESI) Calcd for C 41 H 56 O2PSi4 + ([M+H] + ): 723.3090; Found: 723.3086.

[0055] Example 8: R )-7'-bis[3,5-bis(dicyclohexylmethyl)phenyl]phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0056] The operation is the same as in Example 2, white solid, 154 mg, yield 23%, 1 1H NMR (400 MHz, CDCl3) δ: 1 1H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 5.7, 3.4 Hz, 1H), 7.53 (dd, J = 5.7,3.3 Hz, 1H), 7.29 (d, J = 7.4 Hz, 1H), 7.19 (td, J = 7.5, 2.8 Hz, 2H), 7.13(d, J = 8.1 Hz, 1H), 7.04–6.92 (m, 5H), 6.80 (t, J = 7.4 Hz, 1H), 6.68 (d, J = 7.8 Hz, 1H), 3.90 (dd, J = 15.3, 8.5 Hz, 1H), 3.26 (d, J = 6.2 Hz, 12H),2.97 (t, J = 7.4 Hz, 2H), 2.58 (d, J = 15.3 Hz, 1H), 2.36–2.23 (m, 1H), 2.20–2.09 (m, 1H), 2.07–0.57 (m, 88H). 1313C NMR (101 MHz, CDCl3) δ 166.6, 166.1, 149.6, 147.4, 147.1, 143.7, 139.2, 135.1, 134.2, 134.0, 132.8, 132.7, 131.3, 130.7, 130.5, 130.3, 129.8, 129.6, 129.4, 127.8, 127.0, 126.8, 125.6, 124.5, 123.0, 116.2, 84.6, 64.5, 52.7, 50.5, 42.4, 42.3, 42.2, 42.1, 41.1, 40.9, 39.4, 30.9, 29.5, 28.9, 28.6, 28.6, 28.3, 27.7, 27.0, 27.0, 26.9, 26.5, 26.4, 26.2, 26.1, 26.0, 25.9, 25.9, 25.8, 21.6, 18.1, 13.1, 12.7. 31 31P NMR (162 MHz, CDCl3) δ –20.51. HRMS (ESI) Calcd for C 85 H 120 O7P + ([M+H] + ): 1283.8766; Found: 1283.8763.

[0057] Example 9: R )-7'-Bis(3,5-diphenylphenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0058] The operation is the same as in Example 2, white solid, 136 mg, yield 76%. 1 1H NMR (400 MHz, CDCl3) δ : 1 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J J = 19.6 Hz, 2H), 7.63 (t, J J = 8.3 Hz, 8H), 7.57–7.37 (m, 19H), 7.20 (d, J J = 8.0 Hz, 1H), 7.15–7.07 (m, 1H), 6.58 (d, J J = 4.4 Hz, 2H), 4.61 (dd, J= 15.5, 10.6 Hz, 1H), 3.24–3.01 (m, 3H), 2.58–2.42(m, 1H), 2.37–2.23 (m, 1H). 13 C NMR (101 MHz, CDCl3) δ 168.3, 150.9, 150.8,150.7, 147.3, 147.2, 142.2, 142.1, 142.0, 140.0, 136.5, 135.5, 134.1, 134.0,133.0, 129.8, 129.6, 129.4, 129.3, 129.3, 129.1, 129.0, 128.9, 128.8, 128.6,128.1, 128.1, 127.8, 127.7, 127.6, 127.6, 127.4, 127.3, 126.6, 123.1, 116.6,52.4, 42.4, 40.3, 30.4. 31 P NMR (162 MHz, CDCl3) δ –20.92. Optical rotation: [a]27D =–95 ( c 0.25, CHCl3), melting point: 239–240 ℃ HRMS (ESI) Calcd for C 53 H 40 O2P + ([M+H] + ): 739.2760; Found: 739.2759.

[0059] Example 10: ( R )-7'-Bis(3,5-bis(2,4,6-triisopropylphenyl)phenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0060] The operation is the same as in Example 2, white solid, 224 mg, yield 27%. 1 H NMR (400 MHz, CDCl3) δ: 1 H NMR (400 MHz, CDCl3) δ 7.33 (d, J = 7.1 Hz, 1H), 7.27–7.10 (m, 7H), 7.00(d, J = 15.8 Hz, 10H), 6.91 (s, 1H), 6.66 (d, J = 7.6 Hz, 1H), 6.55 (t,J = 7.4 Hz, 1H), 3.94 (dd, J = 15.2, 8.4 Hz, 1H), 3.02 (dt, J = 14.1, 8.0 Hz, 2H), 2.92 (dq, J = 13.5, 6.8 Hz, 4H), 2.79 (d, J = 15.2 Hz, 1H), 2.65 (ddq, J = 41.7, 13.6, 6.7 Hz, 8H), 2.35 (dt, J = 13.8, 7.1 Hz, 1H), 2.18 (dt, J = 12.8, 7.4 Hz, 1H), 1.31 (dd, J = 10.1, 6.9 Hz, 24H), 1.09–1.00 (m, 24H), 0.95–0.84 (m, 24H). 13 C NMR (101 MHz, CDCl3) δ 166.0, 149.4, 148.7, 148.4, 146.8, 146.7, 145.2, 145.1, 145.1, 144.1, 144.0, 139.6, 139.6, 139.5, 139.4, 135.6, 135.5, 135.4, 135.3, 134.4, 134.3, 130.8, 130.7, 130.6, 130.5, 130.4, 130.3, 129.9, 127.8, 127.2, 125.7, 125.3, 122.8, 119.3, 119.2, 116.1, 50.6, 50.5, 40.9, 40.7, 39.4, 33.2, 33.2, 29.4, 29.3, 29.2, 28.8, 25.8, 23.2, 23.1, 23.0, 23.0, 22.9, 22.9, 22.8, 31 P NMR (162 MHz, CDCl3) δ –18.07. Optical rotation: [a]27D = –14 ( c 0.1, CHCl3), melting point: 174–176 °C, HRMS (ESI) Calcd for C 89 H 112 O2P + ([M + H] +): 1243.8394; Found: 1243.8398.

[0061] Example 11: ( R )-7'-bis[3,5-bis-(diphenylmethyl)phenyl]phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0062] The operation is the same as in Example 2, white solid, 164.7 mg, yield 75%. 1 1H NMR (400 MHz, CDCl3) δ: 1 1H NMR (400 MHz, CDCl3) δ 7.26–7.13 (m, 26H), 7.05 (t, J J = 7.6 Hz, 1H), 6.98–6.87 (m, 17H), 6.83 (dd, J J = 17.6, 1.7 Hz, 2H), 6.71 (ddd, J J = 9.4, 7.6, 3.1 Hz, 3H), 6.55 (dd, J J = 7.3, 1.6 Hz, 2H), 6.22 (td, J J = 7.2, 6.7, 1.9 Hz, 1H), 6.15 (d, J J = 6.9 Hz, 1H), 5.31 (d, J J = 6.6 Hz, 4H), 3.65 (dd, J J = 15.4, 8.9 Hz, 1H), 3.00–2.85 (m, 2H), 2.45 (d, J J = 15.4 Hz, 1H), 2.29–2.18 (m, 1H), 2.10–1.99 (m, 1H). 1313C NMR (101 MHz, CDCl3) δ 167.4, 150.1, 149.2, 148.9, 144.5, 144.4, 143.6, 143.6, 143.6, 143.5, 137.6, 137.4, 136.2, 136.1, 135.4, 133.5, 133.3, 132.2, 132.0, 131.8, 131.6, 131.0, 130.9, 130.6, 129.1, 128.4, 128.1, 127.8, 126.8, 126.8, 126.2, 126.1, 126.1, 125.7, 124.0, 56.5, 56.4, 51.2, 51.2, 40.4, 29.9. 31 31P NMR (162 MHz, CDCl3) δ –21.63. Optical rotation: [α]27D = –70 ( c 0.1, CHCl3), melting point: 105–106 °C HRMS (ESI) Calcd for C 81 H 64 O2P + ([M+H] + ): 1099.4635; Found: 1099.4638.

[0063] Example 12: ( R )-7'-bis{3,5-bis-[bis-(3,5-dimethylphenyl)methyl]phenyl}phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one synthesis:

[0064] The operation is the same as in Example 2, white solid, 130 mg, yield 36%. 1 1H NMR (400 MHz, CDCl3) δ: 1 1H NMR (400 MHz, CDCl3) δ 7.20 (d, J J = 7.4 Hz, 1H), 7.03–6.88 (m, 4H), 6.77(dd, J J = 192.4, 7.1 Hz, 10H), 6.71 (d, J J = 7.8 Hz, 2H), 6.55 (d, J J = 7.4 Hz,3H), 6.53–6.44 (m, 15H), 6.16 (d, J= 4.1 Hz, 2H), 5.12 (s, 4H), 3.68 (dd, J = 15.4, 9.0 Hz, 1H), 2.91 (t, J = 8.1 Hz, 2H), 2.43 (d, J = 15.4 Hz, 1H),2.32–2.23 (m, 1H), 2.13 (d, J = 4.1 Hz, 48H), 2.09–1.94 (m, 1H). 31 31P NMR (162 MHz, CDCl3) δ –21.62. 13 13C NMR (101 MHz, CDCl3) δ 167.5, 150.5, 149.4, 149.2,144.7, 144.6, 143.9, 143.9, 143.8, 140.0, 139.9, 137.5, 137.5, 135.3, 135.1,133.0, 133.0, 131.6, 130.2, 130.2, 130.0, 128.5, 128.2, 127.9, 127.8, 127.3,126.8, 126.8, 125.7, 124.1, 117.2, 77.3, 56.5, 51.5, 51.4, 41.9, 41.7, 40.7,30.1, 28.7, 28.5, 27.6, 27.4, 24.3, 24.2, 21.4, 13.7. 31 31P NMR (162 MHz, CDCl3)δ –21.62. Optical rotation: [α]27D =–72 ( c 0.1, CHCl3), melting point: 132–133 °C HRMS (ESI) Calcd forC 97 H 96 O2P + ([M+H] + ): 1323.7142; Found: 1323.7137.

[0065] Example 13: ( R )-7'-bis{3,5-bis-[bis-(3,5-diisopropylphenyl)methyl]phenyl}phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one synthesis:

[0066] The operation is the same as in Example 2, white solid, 301 mg, yield 60%.1 1H NMR (400 MHz, CDCl3) δ: 1 1H NMR (400 MHz, CDCl3) δ 7.14 (dd, J J = 5.8, 2.6 Hz, 1H), 6.98 (dd, J J = 5.7, 2.2 Hz, 2H), 6.94 (d, J J = 1.7 Hz, 1H), 6.91–6.84 (m, 4H), 6.84–6.78 (m, 8H), 6.69 (dd, J J = 7.4, 1.8 Hz, 3H), 6.64 (dd, J J = 7.1, 1.6 Hz, 8H), 6.59 (dd, J J = 7.0, 1.7 Hz, 8H), 6.06 (d, J J = 8.1 Hz, 1H), 5.74 (t, J J = 7.5 Hz, 1H), 5.16 (d, J J = 4.8 Hz, 4H), 3.77 (dd, J J = 15.3, 9.4 Hz, 1H), 2.94–2.77 (m, 2H), 2.67 (ddt, J J = 9.7, 6.7, 4.8 Hz, 16H), 2.47 (d, J J = 15.3 Hz, 1H), 2.27–2.09 (m, 1H), 2.05–1.92 (m, 1H), 1.12–1.00 (m, 96H). 13C NMR (101 MHz, CDCl3) δ 167.3, 150.0,149.3, 149.0, 148.3, 148.2, 148.2, 148.1, 144.4, 144.4, 144.3, 144.3, 144.2,144.0, 143.8, 143.7, 143.6, 137.1, 137.0, 136.1, 136.0, 135.6, 134.0, 133.8,132.8, 132.6, 131.9, 131.7, 131.0, 130.7, 130.2, 128.4, 127.7, 127.2, 125.6,125.2, 125.1, 125.0, 124.1, 122.0, 121.9, 121.9, 116.5, 57.4, 57.2, 40.3,34.1, 34.0, 34.0, 34.0, 30.0, 24.1, 24.1, 24.0, 24.0. 31 P NMR (162 MHz, CDCl3)δ –22.64. Optical rotation: [a]27D = –66 ( c 0.1, CHCl3), melting point: 88–89 °C HRMS (ESI) Calcd for C 129 H 160 O2P + ([M+H] + ): 1772.2150; Found:.1772.2154.

[0067] Example 14: ( R Synthesis of 7'-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one (cyclooctadiene) iridium chloride complex:

[0068]

[0069] In the glove box, take the ligand ( R)-7'-Bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one, [Ir(COD)Cl]2 (336 mg, 0.5 mmol) was placed in a dry and clean 50 mL Schlenk tube equipped with a magnetic stir bar and sealed and taken out. Under argon, anhydrous dichloromethane (20 mL) was added, and the reaction was stirred at room temperature for 30 min. The solution changed from orange-red to colorless. TLC plate was used to monitor the complexation situation (petroleum ether / ethyl acetate = 5:1). After the reaction, the solvent was removed under vacuum, and column chromatography separation (petroleum ether / ethyl acetate = 5:1 - 1:1) was carried out to obtain the catalyst( R )-7'-Bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one (cyclooctadiene) iridium chloride complex, white solid, 1.0 g, yield 95%. Melting point: 269 - 270 °C. Specific rotation: = –50.8 ( c 0.5,CHCl3), HRMS (ESI) Calcd for C 55 H 71 ClIrNaO4P + ([M + Na] + ): 1077.4300; Found:1077.4260. 1 1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 7.4 Hz, 1H), 7.43 (t, J = 7.6Hz, 1H), 7.36 (t, J = 8.6 Hz, 1H), 6.91 (d, J = 7.8 Hz, 1H), 6.80 (t, J = 7.6Hz, 1H), 5.90 (t, J = 7.4 Hz, 1H), 5.77 (d, J = 11.0 Hz, 1H), 5.30 (d, J =7.6 Hz, 1H), 5.17 (q, J = 6.6 Hz, 1H), 5.03–4.89 (m, 1H), 3.93 (d, J = 4.9Hz, 2H), 3.72 (s, 3H), 3.64 (s, 3H), 3.41–3.23 (m, 1H), 3.09 (td,J = 9.4, 9.0, 4.9 Hz, 2H), 2.89 (dd, J = 16.0, 8.5 Hz, 1H), 2.78–2.50 (m, 4H), 2.40 (dtd, J = 20.0, 12.4, 11.7, 8.8 Hz, 2H), 2.29–2.16 (m, 2H), 1.55–1.13 (m, 36H), -16.79 (d, J = 9.4 Hz, 1H). 13 C NMR (101 MHz, CDCl3) δ 175.5, 161.3, 161.1, 161.1, 150.4, 149.2, 149.0, 147.3, 147.2, 143.3, 131.7, 130.2, 128.4, 127.6, 127.3, 127.1, 126.9, 126.8, 124.3, 123.8, 123.7, 123.2, 122.9, 122.3, 121.2, 115.1, 98.6, 98.4, 98.2, 98.1, 89.5, 78.8, 64.2, 51.9, 51.8, 46.1, 38.0, 37.9, 35.9, 35.4, 34.8, 34.7, 31.9, 30.4, 29.6, 29.4, 28.2, 26.9, 26.8, 26.8, 26.4, 26.3. 31 P NMR (162 MHz, CDCl3) δ 3.22.

[0070] Example 15: Asymmetric Catalytic Hydrogenation( E )-Sodium 3-phenyl-2-butenoate:

[0071]

[0072] Weigh the substrate ( E )-sodium 3-phenyl-2-butenoate (0.3 mmol) in a glove box, and the catalyst ( R)-7'-Bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one (cyclooctadiene) iridium(III) chloride complex (0.0015 mmol) was added to a hydrogenation inner tube equipped with a magnetic stir bar, sealed and removed, and placed in a hydrogenation autoclave. The gas in the reaction autoclave was rapidly replaced with argon three times. Subsequently, 4 mL of a mixed solvent of toluene and methanol (toluene / methanol = 98:2, v / v) was added to the hydrogenation reaction autoclave using a syringe and stirred to dissolve. The gas in the reaction autoclave was rapidly replaced with hydrogen three times, the hydrogen pressure was adjusted to 20 atm, and the reaction was heated in an oil bath at 65 °C for 24 h, and then the hydrogen in the reaction autoclave was slowly released. The reaction solution was evaporated to remove the solvent using a rotary evaporator, and then the product was washed with ethyl acetate (0.5 mL) to obtain the product. 1 The conversion rate was determined by 1H NMR. The product was derivatized with thionyl chloride and ethanol to the corresponding ethyl ester, and then the ee value was determined using chiral high performance liquid chromatography. White solid, yield 99%, 95% ee, specific rotation: = -18.8 ( c 0.5, MeOH), melting point: 205–206 °C 1 1H NMR (400 MHz, CD3OD) δ 7.20–7.09 (m, 4H), 7.01 (tt, J = 5.7, 2.7 Hz, 1H), 3.13(dp, J = 9.2, 6.8 Hz, 1H), 2.36 (dd, J = 13.8, 6.2 Hz, 1H), 2.25 (dd, J =13.8, 9.1 Hz, 1H), 1.17 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 179.9,147.4, 127.8, 127.8, 126.4, 125.4, 37.3, 20.9.HRMS (ESI) Calcd for C 10 H 11 O2 – ([M–Na] – ): 163.0765; Found: 163.0755. HPLC separation conditions: Chiralcel OD-H column (25 cm ´ 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; tR (major) = 9.63 min; t S (minor) = 15.48 min.

[0073] Example 16: Asymmetric catalytic hydrogenation ( E )-Sodium 3-(p-tolyl)-2-butenoate:

[0074]

[0075] The operation was the same as in Example 15. White solid, yield 99%, 95% ee, optical rotation: = -20.4 ( c 0.5, MeOH), melting point: 198–200 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.15 (d, J = 8.1 Hz, 2H), 7.07 (d, J = 7.9 Hz, 2H), 3.21 (dp, J = 9.2, 6.8 Hz, 1H), 2.51–2.31 (m, 2H), 2.29 (s, 3H), 1.26 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.1, 144.3, 134.7, 128.4, 126.3, 36.8, 20.9, 19.6. HRMS (ESI) Calcd for C 11 H 13 O2 – ([M–Na] – ): 177.0921; Found: 177.0913. HPLC separation conditions: Chiralcel OJ-3 column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99:1; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor) = 9.63 min; t 2 (major) = 15.48 min.

[0076] Example 17: Asymmetric catalytic hydrogenation ( E )-Sodium 3-(p-methoxyphenyl)-2-butenoate:

[0077]

[0078] The operation was the same as in Example 15. A white solid was obtained with a yield of 99% and 97% ee. Optical rotation: = -24.8 ( c 0.5, MeOH), melting point: 201–203 °C 1 1H NMR (400 MHz, CD3OD) δ 7.17 (d, J J = 8.6 Hz, 2H), 6.81 (d, J J = 8.7 Hz, 2H), 3.73 (s, 3H), 3.20 (dp, J J = 8.9, 6.8 Hz, 1H), 2.51–2.29 (m, 2H), 1.25 (d, J J = 7.0 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.2, 157.8, 139.4, 127.2, 113.2, 54.2, 36.4, 21.2. HRMS (ESI) Calcd for C 10 H 13 O3 – ([M–Na] – ): 193.0870; Found: 193.0863. HPLC separation conditions: Chiralcel OJ-3 column (25 cm × 0.46 cm ID) + OJ-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99.5:0.5; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (major) = 37.45 min; t 2 (minor) = 41.22 min.

[0079] Example 18: Asymmetric catalytic hydrogenation ( E )-Sodium (E)-3-(4-chlorophenyl)-2-butenoate:

[0080]

[0081] The operation was the same as in Example 15. A white solid was obtained with a yield of 99% and 93% ee. Optical rotation: = -25.6 (c 0.5, MeOH), melting point: 227–229 °C 1 1H NMR (400 MHz, CD3OD) δ 7.26 (s, 3H), 3.25 (dp, J J = 8.5, 6.8 Hz, 1H), 2.52–2.26 (m, 2H), 1.27 (d, J J = 7.0 Hz, 3H). 13 13C NMR (101MHz, CD3OD) δ 179.6, 146.1, 131.0, 128.1, 127.9, 46.6, 36.7, 20.9. HRMS (ESI) Calcd for C 10 H 10 ClO2 – ([M–Na] – ): 197.0375; Found: 197.0370. HPLC separation conditions: AD-3 Chiralcel column (25 cm × 0.46 cm ID) + AD-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99.5:0.5; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor) = 20.75 min; t 2 (major) = 21.60 min.

[0082] Example 19: Asymmetric catalytic hydrogenation( E (S)-Sodium 3-(4-fluorophenyl)-2-butenoate:

[0083]

[0084] The operation was the same as in Example 15. White solid, yield 99%, 96% ee, optical rotation: α = -22.4 ( c 0.5, MeOH), melting point: 206–208 °C 1 1H NMR (400 MHz, CD3OD) δ 7.32–7.20 (m, 2H), 7.02–6.90 (m, 2H), 3.24 (dp, J J = 8.8, 6.9 Hz, 1H), 2.49–2.29 (m, 2H), 1.25 (d,J = 7.0 Hz, 3H). 13 C NMR (101 MHz, CD3OD) δ 180.3, 144.4, 128.2, 127.3, 125.2, 48.7, 43.2, 41.4, 30.9, 30.3, 26.3, 26.3, 26.2. HRMS (ESI) Calcd for C 10 H 10 FO2 – ([M–Na] – ): 181.0661; Found: 181.0670. HPLC separation conditions: OJ-3 Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 90:10; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (major) = 13.51 min; t 2 (minor) = 15.68 min.

[0085] Example 20: Asymmetric catalytic hydrogenation( E )-Sodium 3-(4-bromophenyl)-2-butenoate:

[0086]

[0087] The operation was the same as in Example 15, white solid, yield 99%, 92% ee, optical rotation: = -24.4 ( c 0.5, MeOH), melting point: 245–246 °C 1 H NMR (400 MHz, CD3OD) δ 7.37 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 3.30–3.15 (m, 1H), 2.50–2.28 (m, 2H), 1.26 (d, J = 7.0 Hz, 3H). 13 C NMR (101 MHz, CD3OD) δ 179.6, 146.6, 130.9, 128.5, 118.9, 46.5, 36.8, 20.9. HRMS (ESI) Calcd for C 10 H 10BrO2 – ([M–Na] – ): 240.9870, 242.9849; Found: 240.9875, 242.9853. HPLC separation conditions: AD-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 90:10; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (major) = 11.30 min; t 2 (minor) = 12.79 min.

[0088] Example 21: Asymmetric catalytic hydrogenation ( E )-Sodium 3-(m-tolyl)-2-butenoate:

[0089]

[0090] The operation was the same as in Example 15. White solid, yield 99%, 94% ee, optical rotation: = -24.4 ( c 0.5, MeOH), melting point: 204–206 °C 1 1H NMR (400 MHz, CD3OD) δ 7.12 (t, J = 7.5 Hz, 1H), 7.09–7.00 (m, 2H), 6.94 (d, J = 7.4 Hz, 1H), 3.21 (dp, J = 9.1, 6.8 Hz, 1H), 2.46 (dd, J = 13.8, 6.2 Hz, 1H), 2.35 (dd, [[ID=3�]] J = 13.8, 9.0 Hz, 1H), 2.29 (s, 3H), 1.26 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.1, 147.3, 137.3, 127.7, 127.1, 126.1, 123.4, 46.8, 37.2, 21.0, 20.2. HRMS (ESI) Calcd for C 11 H 13 O2 – ([M–Na]– ): 177.0921; Found:. 177.0913 HPLC separation conditions: OD-HChiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (major) = 8.59 min; t 2 (minor) = 11.76 min.

[0091] Example 22: Asymmetric catalytic hydrogenation( E )-Sodium 3-(m-methoxyphenyl)-2-butenoate:

[0092]

[0093] The operation was the same as in Example 15, white solid, yield 99%, 91% ee, optical rotation: = -21.6( c 0.5,MeOH), melting point: 195–197 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.17 (t, J = 7.9 Hz, 1H),6.89–6.80 (m, 2H), 6.71 (ddd, J = 8.2, 2.5, 0.9 Hz, 1H), 3.78 (s, 3H), 3.23(dp, J = 9.0, 6.8 Hz, 1H), 2.48 (dd, J = 13.9, 6.2 Hz, 1H), 2.37 (dd, J =13.9, 9.0 Hz, 1H), 1.28 (d, J = 7.0 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.1,159.6, 149.0, 128.8, 118.8, 112.2, 110.8, 54.2, 46.7, 37.3, 20.9.HRMS (ESI)Calcd for C 11 H 13 O3 – ([M–Na] –): 193.0870; Found: 193.0863. HPLC separation conditions: OJ-3Chiralcel column (25 cm × 0.46 cm ID) + OJ-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99.5:0.5; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (major) = 12.45 min; t 2 (minor) = 19.00 min.

[0094] Example 23: Asymmetric catalytic hydrogenation( E )-Sodium 3-(m-chlorophenyl)-2-butenoate:

[0095]

[0096] The operation was the same as in Example 15. White solid, yield 99%, 86% ee, optical rotation: α = -12.4( c c 0.5, MeOH), melting point: 197–199 °C 1 1H NMR (400 MHz, CD3OD) δ 7.35 (ddd, J J = 12.1, 7.9, 1.5 Hz, 2H), 7.25 (td, J J = 7.6, 1.4 Hz, 1H), 7.13 (td, J J = 7.6, 1.7 Hz, 1H), 3.88–3.68 (m, 1H), 2.56 (dd, J J = 14.2, 5.6 Hz, 1H), 2.39 (dd, J J = 14.2, 9.5 Hz, 1H), 1.27 (d, J J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 179.6, 144.3, 129.0, 127.0, 126.8, 126.8, 44.6, 33.2, 19.8. HRMS (ESI) Calcd for C 10 H 10 ClO2 – ([M–Na] –): 197.0375; Found: 197.0369. HPLC separation conditions: IC-3 Chiralcel column (25 cm × 0.46 cm ID) × 2; n-hexane / isopropanol = 99.5:0.5; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (major) = 23.63 min; t 2 (minor) = 15.04 min.

[0097] Example 24: Asymmetric catalytic hydrogenation( E ())-3-o-Tolyl-2-butene sodium

[0098]

[0099] The operation was the same as in Example 15. White solid, yield 99%, 94% ee, specific rotation: = -13.2( c 0.5, MeOH), melting point: 206–208 °C 1 1H NMR (400 MHz, CD3OD) δ 7.21 (d, J = 7.7 Hz, 1H), 7.14–7.05 (m, 2H), 7.00 (td, J = 7.4, 1.4 Hz, 1H), 3.53 (dp, J = 9.3, 6.7 Hz, 1H), 2.47 (dd, J = 14.0, 5.9 Hz, 1H), 2.42–2.32 (m, 4H), 1.23 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.2, 145.3, 134.8, 129.7, 125.7, 125.1, 124.8, 45.7, 32.2, 20.5, 18.3. HRMS (ESI) Calcd for C 11 H 13 O2 – ([M–Na] –): 177.0921; Found: 177.0912. HPLC separation conditions: OJ-3 Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 90:10; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (major) = 13.96 min; t 2 (minor) = 16.00 min.

[0100] Example 25: Asymmetric catalytic hydrogenation ( E )-Sodium 3-(o-methoxyphenyl)-2-butenoate:

[0101]

[0102] The operation was the same as in Example 15. White solid, yield 99%, 90% ee, specific rotation: = -7.6( c 0.5, MeOH), melting point: 153–155 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.20 (dd, J = 7.5, 1.7 Hz, 1H), 7.13 (ddd, J = 8.2, 7.4, 1.7 Hz, 1H), 6.94–6.82 (m, 2H), 3.82 (s, 3H), 3.74–3.60 (m, 1H), 2.54 (dd, J = 13.9, 5.5 Hz, 1H), 2.36 (dd, J = 14.0, 9.8 Hz, 1H), 1.24 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.4, 156.9, 135.3, 126.3, 126.2, 120.1, 110.1, 54.3, 44.8, 30.4, 19.6. HRMS (ESI) Calcd for C 11 H 13 O3 – ([M–Na] –): 193.0870; Found: 193.0862. HPLC separation conditions: OJ-3 Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (major) = 13.87 min; t 2 (minor) = 15.33 min.

[0103] Example 26: Asymmetric catalytic hydrogenation ( E )-Sodium (3-O-chlorophenyl)-2-buteneoate:

[0104]

[0105] The operation was the same as in Example 15. White solid, yield 99%, 88% ee, specific rotation: = -36 ( c 0.5, MeOH), melting point: 146–149 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.29–7.15 (m, 3H), 7.13 (dt, J = 7.6, 1.9 Hz, 1H), 3.23 (dt, J = 8.6, 6.8 Hz, 1H), 2.44 (dd, J = 13.9, 6.7 Hz, 1H), 2.35 (dd, J = 13.9, 8.6 Hz, 1H), 1.26 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 179.6, 149.7, 133.6, 129.4, 126.6, 125.5, 125.0, 46.4, 37.1, 20.9. HRMS (ESI) Calcd for C 10 H 10 ClO2 – ([M–Na] –): 197.0375; Found: 197.0368. HPLC separation conditions: AD-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor)=8.16 min; t 2 (major) = 9.43 min.

[0106] Example 27: Asymmetric catalytic hydrogenation ( E )-Sodium 3-(trifluoromethyl)phenyl-2-butenoate:

[0107]

[0108] The operation was the same as in Example 15. White solid, yield 99%, 96% ee, optical rotation: = -20 ( c 0.5, MeOH), melting point: 273–276 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.69–7.51 (m, 3H), 7.37–7.25 (m, 1H), 3.80–3.67 (m, 1H), 2.58–2.40 (m, 2H), 1.32 (d, J = 6.7 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 179.2, 146.7, 131.9, 127.8, 127.2 (d, J = 28.7 Hz), 125.6, 125.0 (q, J = 5.9 Hz), δ 124.7 (q, J = 273.4 Hz), 45.9, 32.4, 21.4. HRMS (ESI) Calcd for C 11 H 10 F3O2 – ([M–Na] –): 231.0638; Found: 231.0636. HPLC separation conditions: OJ-3 Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 90:10; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 220 nm; t 1 (major) = 9.35 min; t 2(minor) = 10.06 min.

[0109] Example 28: Asymmetric catalytic hydrogenation ( E )-Sodium 3,4-diphenyl-2-buteneate:

[0110]

[0111] The operation was the same as in Example 15. White solid, yield 99%, 92% ee, specific rotation: = 55.6 ( c 0.5, MeOH), melting point: 149 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.10 (dt, J = 26.4, 8.0 Hz, 8H), 7.00 (d, J = 7.5 Hz, 2H), 3.48–3.36 (m, 1H), 3.01 (dd, J = 13.4, 5.7 Hz, 1H), 2.81 (dd, J = 13.4, 9.1 Hz, 1H), 2.59–2.43 (m, 2H). 13 13C NMR (101 MHz, CD3OD) δ 179.7, 144.7, 140.5, 128.9, 127.5, 127.5, 127.4, 125.4, 125.2, 45.1, 44.5, 42.5. HRMS (ESI) Calcd for C 16 H 15 O2 – ([M–Na] –): 239.1078; Found: 239.1075. HPLC separation conditions: OD-3 Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99.5:0.5; temperature: 20 °C; flow rate: 210 mL / min; detection wavelength: 210 nm; t 1 (major) = 17.88 min; t 2 (minor) = 25.23 min.

[0112] Example 29: Asymmetric catalytic hydrogenation( E ())-Sodium 3-cyclopropyl-3-phenylacrylate:

[0113]

[0114] The operation was the same as in Example 15. White solid, yield 99%, 94% ee, optical rotation: = 28.8 ( c 0.5, MeOH), melting point: 245–247 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.31–7.18 (m, 4H), 7.12 (t, J = 7.1 Hz, 1H), 2.62 (dd, J = 13.6, 7.4 Hz, 1H), 2.54 (dd, J = 13.6, 7.7 Hz, 1H), 2.45–2.34 (m, 1H), 1.08–0.94 (m, 1H), 0.54 (dp, J = 10.1, 3.6 Hz, 1H), 0.34 (tt, J = 8.8, 4.2 Hz, 2H), 0.08 (dh, J = 9.1, 4.2 Hz, 1H). 13 13C NMR (101 MHz, CD3OD) δ 178.4, 144.0, 126.0, 125.6, 123.8, 43.4, 15.6, 2.8, 1.4. HRMS(ESI) Calcd for C 12 H 13 O2 – ([M–Na] –):189.0921; Found: 189.0914. HPLC separation conditions: OD-H Chiralcel column (25 cm ´ 0.46 cm ID); n-hexane / isopropanol = 99:1; temperature: 20°C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (major) = 8.92 min; t 2 (minor) = 14.45min.

[0115] Example 30: Asymmetric catalytic hydrogenation ( E )-3-cyclohexyl-2-butenoic acid sodium

[0116]

[0117] The operation was the same as in Example 15, and the product was a white solid with a yield of 99%, 90% ee, and optical rotation: = -27.2 ( c 0.5, MeOH), melting point: 317–320 °C, 1 H NMR (400 MHz, CD3OD) δ 7.27–7.16 (m, 4H), 7.16–7.09(m, 1H), 2.96 (dt, J = 9.0, 6.7 Hz, 1H), 2.70 (dd, J = 14.2, 6.4 Hz, 1H),2.43 (dd, J = 14.2, 9.0 Hz, 1H), 1.88 (dt, J = 12.7, 3.2 Hz, 1H), 1.75 (ddt, J = 12.5, 4.8, 2.4 Hz, 1H), 1.69–1.57 (m, 2H), 1.56–1.45 (m, 2H), 1.33–0.93 (m, 4H), 0.89–0.76 (m, 1H). 13 C NMR (101 MHz, CD3OD) δ 180.5, 144.4, 128.2,127.3, 125.3, 48.7, 43.2, 41.4, 31.0, 30.3, 26.4, 26.3, 26.3. HRMS (ESI)Calcd for C 15 H 19 O2 –([M–Na] – ): 231.1391; Found: 231.1388. HPLC separation conditions: OD-H Chiralcel column (25 cm ´ 0.46 cm ID); n-hexane / isopropanol = 99:1; temperature: 20°C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor) = 11.28 min; t 2 (major) = 12.58 min.

[0118] Example 31: Asymmetric catalytic hydrogenation ( E )-3-(2-naphthyl)-2-butenoic acid sodium:

[0119]

[0120] The operation was the same as in Example 15, and the product was a white solid with a yield of 99%, 91% ee, and optical rotation: = 4.8 ( c 0.5, MeOH), melting point: 195–198 °C, 1 H NMR (400 MHz, CD3OD) δ 8.33 (d, J = 8.5 Hz, 1H),7.81 (dd, J = 8.2, 1.3 Hz, 1H), 7.66 (d, J = 7.9 Hz, 1H), 7.51 (ddd, J = 8.5,6.7, 1.5 Hz, 1H), 7.47–7.36 (m, 3H), 4.19 (ddd, J = 9.8, 7.0, 5.1 Hz, 1H),2.74 (dd, J = 14.2, 5.0 Hz, 1H), 2.49 (dd, J = 14.2, 9.8 Hz, 1H), 1.45 (d, J = 6.8 Hz, 3H). 1313C NMR (101 MHz, CD3OD) δ 180.2, 143.3, 134.1, 131.3, 128.4, 125.9, 125.3, 125.2, 124.8, 123.1, 121.9, 46.1, 31.5, 20.5. HRMS (ESI) Calcd for C 14 H 13 O2 – ([M–Na] – ): 213.0921 ; Found: 213.0924. HPLC separation conditions: OD-HChiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (major) = 5.55 min; t 2 (minor) = 18.50 min.

[0121] Example 32: ( Z )-Sodium 5-methoxy-5-oxo-3-phenyl-2-pentenoate

[0122]

[0123] The operation was the same as in Example 15. White solid, yield 99%, 86% ee, optical rotation: = 3.2 ( c 0.5, MeOH), melting point: 148–150 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.33–7.17 (m, 4H), 7.18–7.07 (m, 1H), 3.67–3.55 (m, 1H), 3.50 (s, 3H), 2.80 (dd, J = 15.2, 5.6 Hz, 1H), 2.61 (dd, J = 15.2, 9.7 Hz, 1H), 2.47 (d, J = 8.2 Hz, 2H). 1313C NMR (101 MHz, CD3OD) δ 178.9, 173.1, 144.1, 127.9, 127.0, 125.9, 50.4, 44.6, 40.2, 39.6. HRMS (ESI) Calcd for C 12 H 13 O4 – ([M–Na] – ): 221.0(819); Found: 221.0816. HPLC separation conditions: OJ-3 Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 90:10; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (minor) = 32.89 min; t 2 (major) = 38.73 min.

[0124] Example 33: ( E )-2-Methyl-3-phenylacrylate sodium

[0125]

[0126] The operation was the same as in Example 15, white solid, yield 99%, 81% ee, 1 1H NMR (400 MHz, CD3OD) δ 7.28–7.23 (m, 4H), 7.18–7.09 (m, 1H), 3.11–2.96 (m, 1H), 2.63–2.49 (m, 2H), 1.08 (d, J J 10 H 17 O2 – ([M–Na] – ): 169.1234; Found: 169.1225. HPLC separation conditions: OB-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99.5:0.5; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 220 nm; t 1 (major) = 11.72 min; t 2 Note: In the original text, there seems to be a formatting issue in the "HRMS (ESI) Calcd for C " part where the numbers might be cut off. I've tried to make sense of it in the translation. Also, the symbol "J" in the "1H NMR" part might be a formatting error in the original, but I've left it as is in the translation. The "()" around the "minor" and "major" retention times in the HPLC conditions seem a bit odd in the original, but again, I've translated as is.(minor) = 14.07 min.

[0127] Example 34: ( E )-Sodium 3-phenyl-2-heptenoate

[0128]

[0129] The operation was the same as in Example 15. A white solid was obtained with a yield of 99% and 91% ee. Optical rotation: = -3.2 ( c 0.5, MeOH), melting point: 300–302 °C, 1 1H NMR (400 MHz, CD3OD) δ 7.22 (d, J = 7.1 Hz, 4H), 7.16–7.06 (m, 1H), 3.14–2.99 (m, 1H), 2.53–2.34 (m, 2H), 1.79–1.66 (m, 1H), 1.66–1.48 (m, 1H), 1.38–0.99 (m, 4H), 0.82 (t, J = 7.2 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 180.1, 145.7, 127.7, 127.2, 125.4, 45.8, 43.1, 35.6, 29.5, 22.3, 13.0. HRMS (ESI) Calcd for C 13 H 17 O2 – ([M–Na] – ): 205.1234; Found: 205.1227 HPLC separation conditions: AD-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 90:10; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (minor) = 8.43 min; t 2 (major) = 9.96 min.

[0130] Example 35: Asymmetric catalytic hydrogenation ( E )-Sodium 3-cyclopropyl-3-(3-methoxyphenyl)acrylate:

[0131]

[0132] Weigh the substrate ([[]] E )-Sodium 3-cyclopropyl-3-(3-methoxyphenyl)acrylate (1.2 g, 5 mmol), the catalyst ([[]] R )-7'-Bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one (cyclooctadiene) iridium chloride complex (10 mg, 0.01 mmol), and acetic acid (0.2 mmol) into a hydrogenation inner tube equipped with a magnetic stir bar, seal it and take it out, and place it in a hydrogenation autoclave. Quickly displace the gas in the reaction autoclave with argon three times, and then use a syringe to add 125 mL of a mixed solvent of toluene and methanol (toluene / methanol = 98:2, v / v) to the hydrogenation reaction autoclave, and stir to dissolve. Quickly displace the gas in the reaction autoclave with hydrogen three times, adjust the hydrogen pressure to 20 atm, place it in an oil bath at 65 °C and heat for 48 h, and then slowly release the hydrogen in the reaction autoclave. The reaction solution is evaporated to remove the solvent with a rotary evaporator, and then the product is washed with ethyl acetate (0.5 mL). 1 The conversion rate was determined by 1H NMR. The product was derivatized with thionyl chloride and ethanol into the corresponding ethyl ester, and then the ee value was determined by chiral high performance liquid chromatography. The product was a white solid, 1.2 g, yield 99%, 95% ee, specific rotation: = 26.0 ( c 0.5, MeOH), melting point: 196 - 198 °C. 1 1H NMR (400 MHz, CD3OD) δ 7.20–7.09 (m, 4H), 7.01 (tt, J = 5.7, 2.7 Hz, 1H), 3.13 (dp, J = 9.2, 6.8 Hz, 1H),2.36 (dd, J = 13.8, 6.2 Hz, 1H), 2.25 (dd, J = 13.8, 9.1 Hz, 1H), 1.17 (d, J = 6.9 Hz, 3H). 13 13C NMR (101 MHz, CD3OD) δ 179.9, 147.4, 127.8, 127.8, 126.4,125.4, 37.3, 20.9. HRMS (ESI) Calcd for C 13 H 15 O3 – ([M–Na] – ​​): 219.1027; Found: 219.1029. HPLC separation conditions: OD-H Chiralcel column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 99:1; temperature: 20 °C; flow rate: 1.0 mL / min; detection wavelength: 210 nm; t 1 (major) = 6.93 min; t 2 (minor) = 12.02 min.

[0133] Example 36: Asymmetric catalytic hydrogenation of sodium ( E )-3-phenyl-2-butenoate at low catalyst loading:

[0134]

[0135] In a glove box, weigh out the substrate sodium ( E )-3-phenyl-2-butenoate (7.5 mmol), the catalyst ( R )-7'-bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one (cyclooctadiene) iridium chloride complex (0.0015 mmol), ( E )-3-phenyl-2-butenoic acid (0.3 mmol%) and add them to a hydrogenation inner tube equipped with a magnetic stir bar and seal it. Take it out and place it in a hydrogenation autoclave. Quickly displace the gas in the reaction autoclave with argon three times, and then use a syringe to add 1000 mL of a mixed solvent of toluene and methanol (toluene / methanol = 98:2, v / v) to the hydrogenation reaction autoclave and stir to dissolve. Quickly displace the gas in the reaction autoclave with hydrogen three times, adjust the hydrogen pressure to 20 atm, place it in an oil bath at 65 °C and heat the reaction for 3 days, and then slowly release the hydrogen in the reaction autoclave. The reaction solution is evaporated to remove the solvent with a rotary evaporator, and then the product is washed with ethyl acetate (2 mL) to obtain the product. 1 The conversion rate is determined by 1H NMR. The product is derivatized with thionyl chloride and ethanol to the corresponding ethyl ester and then the ee value is determined using chiral high performance liquid chromatography. White solid, yield 99%, 93% ee.

[0136] Example 37: Asymmetric catalytic hydrogenation of sodium ( E )-3-phenyl-3-p-tolylacrylate:

[0137]

[0138] In a glove box, weigh out the substrate E) Sodium 3-phenyl-3-(p-tolyl)acrylate (0.3 mmol), catalyst( R ) (7'-Bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphino-2',3'-dihydrospiro[chromene-4,1'-indene]-2-one)(cyclooctadiene)iridium(III) chloride complex (0.0015 mmol) was added to a sealed hydrogenation inner tube equipped with a magnetic stir bar, removed, and placed in a hydrogenation autoclave. The gas in the reaction autoclave was rapidly replaced with argon three times, and then 4 mL of a mixed solvent of toluene and methanol (toluene / methanol = 95:5, v / v) was added to the hydrogenation reaction autoclave using a syringe and stirred to dissolve. The gas in the reaction autoclave was rapidly replaced with hydrogen three times, the hydrogen pressure was adjusted to 20 atm, and the reaction was stirred at room temperature (25 - 30 °C). After the reaction was completed, the hydrogen in the reaction autoclave was slowly released. The reaction solution was concentrated to remove the solvent using a rotary evaporator, and then the product was washed with ethyl acetate (0.5 mL). 1 The conversion was determined by 1H NMR. The product was derivatized with thionyl chloride and ethanol to the corresponding ethyl ester, and the ee value was determined using chiral high performance liquid chromatography.

[0139] Example 38: E ) Asymmetric catalytic hydrogenation of sodium 3-phenyl-3-(p-methoxyphenyl)acrylate:

[0140]

[0141] The operation was the same as in Example 37. A white solid was obtained with a yield of 99% and 92% ee. Optical rotation: αD = 0.4 ( c c 0.5, MeOH), melting point: 310 - 312 °C 1 1H NMR (400 MHz, CD3OD) δ 7.22 (dt, J J = 23.6, 8.1 Hz, 6H), 7.09 (t, J J = 7.2 Hz, 1H), 6.78 (d, J J = 8.4 Hz, 2H), 4.51 (t, J J = 7.9 Hz, 1H), 3.70 (s, 3H), 2.85 (d, J J = 7.9 Hz, 2H). 13 13C NMR (101 MHz, CD3OD) δ 179.2, 157.9, 145.6, 137.3, 128.5, 127.8, 127.5, 125.4, 113.2, 54.2, 47.3, 44.5. HRMS (ESI) Calcd for C 16 H15 O3 – ([M–Na] – ): 255.1027; Found: 255.1026. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (minor) = 6.90 min; t 2 (major) = 8.6 min.

[0142] Example 39: ( E )-Sodium 3-phenyl-3-(4-chlorophenyl)acrylate asymmetric catalytic hydrogenation:

[0143]

[0144] The operation was the same as in Example 37. White solid, yield 99%, 87% ee, optical rotation: = 0.4 ( c 0.5, MeOH), melting point: 242 - 244 °C 1 1H NMR (400 MHz, CD3OD) δ 7.29–7.17 (m, 8H), 7.17–7.08 (m, 1H), 4.54 (t, J = 7.9 Hz, 1H), 2.86 (d, J = 8.0 Hz, 2H). 13 13C NMR (101 MHz, CD3OD) δ 178.7, 144.7, 144.0, 131.2, 129.2, 128.0, 127.8, 127.5, 125.7, 47.5, 44.2. HRMS (ESI) Calcd for C 15 H 12 ClO2 – ([M–Na] – ): 259.0531; Found: 259.0532. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1(minor) = 5.55 min; t 2 (major)= 7.17 min.

[0145] Example 39: ( E ) Asymmetric catalytic hydrogenation of sodium (E)-3-phenyl-3-(4-fluorophenyl)acrylate:

[0146]

[0147] The operation was the same as in Example 37. A white solid was obtained with a yield of 99% and 89% ee. Optical rotation: = -2.4 ( c 0.5,MeOH), melting point: 242 - 245 °C 1 1H NMR (400 MHz, CD3OD) δ 7.32–7.18 (m, 6H), 7.16–7.07(m, 1H), 6.95 (t, J = 8.8 Hz, 2H), 4.55 (t, J = 7.9 Hz, 1H), 2.86 (d, J = 8.0Hz, 2H). 13 13C NMR (101 MHz, CD3OD) δ 178.8, 162.4, 160.0, 145.0, 141.1 (d, J =3.1 Hz), 129.2, 129.1, 127.9, 127.5, 125.6, 114.4, 114.2, 44.4.HRMS (ESI)Calcd for C 15 H 12 FO2 – ([M–Na] – ): 243.0827; Found: 243.0825. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID)+ Chiralcel IA-3 column (25 cm ×0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor) = 26.7 min; t 2 (major) = 31.8 min.

[0148] Example 40: ( E ) Asymmetric catalytic hydrogenation of sodium (E)-3-phenyl-3-(p-fluorophenyl)acrylate:

[0149]

[0150] The operation was the same as in Example 37. A white solid was obtained with a yield of 99% and 88% ee. Optical rotation: = -0.4 ( c 0.5, MeOH), melting point: 245 - 247 °C 1 1H NMR (400 MHz, CD3OD) δ 7.41–7.32 (m, 2H), 7.30–7.16 (m, 6H), 7.16–7.08 (m, 1H), 4.54 (t, J = 7.9 Hz, 1H), 2.87 (d, J = 8.0 Hz, 2H). 13 13C NMR (101 MHz, CD3OD) δ 178.7, 144.6, 144.4, 130.8, 129.6, 128.0, 127.5, 125.8, 119.2, 47.6, 44.1. HRMS (ESI) Calcd for C 15 H 12 BrO2 – ([M–Na] – ): 303.0026, 305.0006; Found: 303.0027, 306.0036. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (minor) = 5.77 min; t 2 (major) = 7.50 min.

[0151] Example 41: ( E ) Asymmetric catalytic hydrogenation of sodium (E)-3-phenyl-3-(m-methylphenyl)acrylate:

[0152]

[0153] The operation was the same as in Example 37. A white solid was obtained with a yield of 99% and 88% ee. Optical rotation: = -4.8 (c 0.5, MeOH), melting point: 252 - 254 °C 1 1H NMR (400 MHz, CD3OD) δ 7.27 (d, J J = 7.3 Hz, 2H), 7.21 (t, J J = 7.6 Hz, 2H), 7.13–7.03 (m, 4H), 6.92 (d, J J = 7.0 Hz, 1H), 4.52 (t, J J = 7.9 Hz, 1H), 2.87 (d, J J = 7.9 Hz, 2H), 2.25 (s, 3H). 13 13C NMR (101 MHz, CD3OD) δ 179.0, 145.3, 145.1, 137.3, 128.3, 127.7, 127.7, 127.5, 126.1, 125.4, 124.6, 48.0, 44.3, 20.1. HRMS (ESI) Calcd for C 16 H 15 O2 – ([M–Na] – ): 239.1078; Found: 239.1076. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (minor) = 5.68 min; t 2 (major) = 6.27 min.

[0154] Example 42: ([[]] E )-Sodium 3-phenyl-3-(m-methoxyphenyl)acrylate asymmetric catalytic hydrogenation:

[0155]

[0156] The operation is the same as in Example 37, white solid, yield 99%, 88% ee, optical rotation: / c = -2.4 ( c 0.5, MeOH), melting point: 241 - 245 °C. 11H NMR (400 MHz, CD3OD) δ 7.31–7.19 (m, 4H), 7.16–7.06(m, 2H), 6.89–6.80 (m, 2H), 6.68 (ddd, J J = 8.2, 2.6, 0.9 Hz, 1H), 4.53 (t, J J = 7.9 Hz, 1H), 3.71 (s, 3H), 2.87 (d, J J = 7.9 Hz, 2H). 13 13C NMR (101 MHz,CD3OD) δ 179.0, 159.6, 146.8, 145.1, 128.7, 127.8, 127.5, 125.5, 119.9,113.4, 110.9, 54.1, 48.1, 44.2. HRMS (ESI) Calcd for C 16 11 15 H – ([M–Na] – ):255.1027; Found: 255.1027. HPLC separation conditions: Chiralcel OD-H column (25 cm´ 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (minor) = 6.90 min; t 2 (major) = 8.55 min.

[0157] Example 43: Asymmetric catalytic hydrogenation of ( E )-sodium 3-phenyl-3-(p-chlorophenyl)acrylate:

[0158]

[0159] The operation was the same as in Example 37. White solid, yield 99%, 84% ee, optical rotation: α = -4.4 ( c c 0.5,MeOH), melting point: 253-255 °C. 1 1H NMR (400 MHz, MeOD) δ 7.31–7.17 (m, 7H), 7.17–7.07(m, 2H), 4.55 (t, J J = 7.94 Hz, 1H), 2.87 (d,J = 7.96 Hz, 2H). 13 C NMR (101MHz, MeOD) δ 178.5, 147.6, 144.4, 133.7, 129.4, 128.1, 127.7, 127.5, 126.1,125.9, 125.7, 48.5, 44.0. HRMS (ESI) Calcd for C 15 H 12 ClO2 – ([M–Na] – ): 259.0531; Found: 259.0532. HPLC separation conditions: Chiralcel OD-H column (25 cm ´ 0.46 cm ID) + Chiralcel IA-3 column (25 cm ´ 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor) = 27.73 min; t 2 (major) = 35.88 min.

[0160] Example 44: ( E )-Sodium 3-phenyl-3-o -tolylacrylate asymmetric catalytic hydrogenation:

[0161]

[0162] The operation is the same as in Example 37, white solid, yield 99%, 97% ee, optical rotation: = 76 ( c 0.5, MeOH), melting point: 276 - 278 °C. 1 H NMR (400 MHz, CD3OD) δ 7.23–7.16 (m, 4H), 7.17–7.08(m, 2H), 7.08–7.02 (m, 2H), 4.78 (t, J = 7.9 Hz, 1H), 2.85 (qd, J = 14.7, 7.9 Hz, 2H), 2.24 (s, 3H). 1313C NMR (101 MHz, CD3OD) δ 179.2, 145.0, 142.5, 136.2, 129.9, 127.7, 126.4, 125.6, 125.4, 125.4, 44.8, 44.2, 18.7. HRMS (ESI) Calcd for C 16 H 15 O2 – ([M–Na] – ): 239.1078; Found: 239.1076. HPLC separation conditions: Chiralcel OD-H column (25 cm ´ 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (major) = 5.98 min; t 2 (minor) = 7.43 min.

[0163] Example 45: ( E )-Sodium 3-phenyl-3-(o-methoxyphenyl)acrylate asymmetric catalytic hydrogenation:

[0164]

[0165] The operation was the same as in Example 37. White solid, yield 99%, 90% ee, optical rotation: = -11.2 ( c 0.5, MeOH), melting point: 260 - 262 °C 1 1H NMR (400 MHz, CD3OD) δ 7.28 (d, J = 7.6 Hz, 3H), 7.20 (t, J = 7.5 Hz, 2H), 7.14 (t, J = 7.8 Hz, 1H), 7.11–7.05 (m, 1H), 6.93–6.82 (m, 2H), 4.99 (t, J = 8.2 Hz, 1H), 3.72 (s, 3H), 2.97–2.79 (m, 2H). 13CNMR (101 MHz, CD3OD) δ 179.4, 157.0, 145.2, 133.3, 127.7, 127.5, 127.4,126.8, 125.1, 119.9, 110.4, 54.4, 43.3, 41.1.HRMS (ESI) Calcd for C 16 H 15 O3 – ([M–Na] – ): 255.1027; Found: 255.1027. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (major) = 6.39 min; t 2 (minor) = 15.15 min.

[0166] Example 46: Asymmetric catalytic hydrogenation of ( E )-3-phenyl-3-o-chlorophenyl acrylate sodium:

[0167]

[0168] The operation is the same as in Example 37, white solid, yield 99%, 89% ee, optical rotation: = 26 ( c 0.2,MeOH), melting point: 280 - 284 °C 1 H NMR (400 MHz, CD3OD) δ 7.46 (dd, J = 7.8, 1.7 Hz, 1H),7.36–7.28 (m, 2H), 7.28–7.19 (m, 4H), 7.13 (dtd, J = 7.2, 5.1, 2.3 Hz, 2H),5.10 (t, J = 8.0 Hz, 1H), 2.99–2.83 (m, 2H). 1313C NMR (101 MHz, CD3OD) δ 178.6, 143.8, 142.1, 133.9, 129.2, 128.5, 127.8, 127.1, 126.5, 125.6, 44.5, 43.8. HRMS (ESI) Calcd for C 15 H 12 ClO2 – ([M–Na] – ): 259.0531; Found: 259.0533. HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID) + Chiralcel IA-3 column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 98:2; temperature: 20 °C; flow rate: 0.5 mL / min; detection wavelength: 210 nm; t 1 (minor) = 6.40 min; t 2 (major) = 8.62 min.

[0169] Example 47: Asymmetric catalytic hydrogenation of ( Z )-sodium 3-phenyl-3-(p-tolyl)acrylate:

[0170]

[0171] The operation was the same as in Example 37. White solid, yield 99%, 92% ee, specific rotation: = -6.6 ( c 1, MeOH). HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (minor) = 4.85 min; t 2 (major) = 6.40 min.

[0172] Example 48: Asymmetric catalytic hydrogenation of ( Z )-sodium 3-phenyl-3-(p-methoxyphenyl)acrylate:

[0173]

[0174] The operation was the same as in Example 37. A white solid was obtained with a yield of 99% and 91% ee. Optical rotation: = -7.6 ( c 1, MeOH). HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (major) = 6.89 min; t 2 (minor) = 8.55 min.

[0175] Example 49: Asymmetric catalytic hydrogenation of ( Z )-sodium 3-phenyl-3-(4-chlorophenyl)acrylate:

[0176]

[0177] The operation was the same as in Example 37. A white solid was obtained with a yield of 99% and 84% ee. Optical rotation: = -2.0 ( c 1, MeOH). HPLC separation conditions: Chiralcel OD-H column (25 cm × 0.46 cm ID); n-hexane / isopropanol = 95:5; temperature: 20 °C; flow rate: 1 mL / min; detection wavelength: 210 nm; t 1 (major) = 5.54 min; t 2 (minor) = 7.14 min.

Claims

1. A chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex, characterized in that It has the following general formula (I): In the general formula (I): R 1 is an aryl group, R 2 is a halogen atom; the aryl group is a phenyl group which is substituted or unsubstituted by an alkyl group or an alkoxy group, wherein the alkyl group is a methyl group, an ethyl group, a propyl group or a butyl group; the alkoxy group is a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

2. The method for synthesizing the chiral spiro[chroman-4,1'-dihydroindene] bidentate ligand iridium complex according to claim 1, characterized in that It is synthesized by the following route: ； The specific steps are: Step 1: Starting material ( R )-7′-hydroxy-2′,3′-dihydrospiro[chroman-4,1′-indene]-2-one (R)-1 is reacted with a triflate reagent in an organic solvent under the promotion of a base at a temperature range of 0-60°C to obtain (R)-7'-trifluoromethylsulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one (R)-2; Step 2: ( R )-7'-trifluoromethylsulfonyloxy-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one (R)-2 undergoes a coupling reaction with a diarylphosphine oxide in an organic solvent, a base, and a temperature range of 0-60 °C under the catalysis of a phosphine ligand and palladium acetate, and is subsequently reduced under the conditions of silane and a base to obtain the target ligand (R)-7'-diarylphosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one (R)-II; Step 3: Ligand ( R )-7'-diarylphosphino-2',3'-dihydrospiro[chroman-4,1'-indene]-2-one (R)-II reacts with an iridium metal precursor in an organic solvent at a temperature range of 0-60 °C to obtain a catalyst (I).

3. The synthesis method according to claim 2, characterized in that The organic solvent in step 1 and step 2 is one or more of dichloromethane, toluene, tetrahydrofuran and methanol.

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